Water-insoluble azo-dyestuffs



Patented Oct. 20, 1936 PATENT OFFIQE WATER-INSOLUBLE AZO-DYE'STUFFS Ernst Fischer, Offenbach-on-the-Main, Germany, assignor to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application May 16, 1935, Serial No. 21,905. In Germany May 19, 1934 4 Claims.

The present invention relates to water-insoluble azo-dyestufis; more particularly it relates to dyestufis of the following general formula wherein the naphthalene nucleus may contain further substituents, X stands for an alkyl or alkoxy group, R for hydrogen, an alkyl, aryl, aralkyl or hydroaromatic radical and R1 and R2 mean hydrogen, alkyl, aryl, aralkyl or hydroaromatic radicals, or R1 and R2 are connected with each other to form a heterocyclic ring system, R1 (or R2) not being allowed to stand for hydrogen in case R2 (or R1) represents an aryl radical.

I have found that valuable red pigment dyestufis are obtainable by coupling the diazo compounds of bases of the following general formula:

wherein X stands for an alkyl or alkoxy group and R for hydrogen, an alkyl, aryl, aralkyl or hydro-aromatic radical, with 2,3-hydroxynaphthoic acid derivatives of the general formula:

(or R1) represents an aryl radical, only such components being used as do not contain groups The dyestuffs thus obtained are distinguished.

by properties of fastness which make them suitable for use on an industrial scale for the production of lakes which are fast to oils and to light, by conducting the coupling operation in presence of a substratum; the dyestuffs being practically insoluble in natural rubber or in synthetic products having properties similar. to those of natural rubber, they are particularly useful in the rubber industry since they do not bleed in the production and treatment of rubber articles. By incorporating the dyestuffs with rubber products mixtures are obtained which are fast to vulcanization and to light.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto: Y

(1) 10.8 grams of B-amino-l-methoxybenzenel-sulfonic acid-methylamide are diazotized in the usual manner. Thereupon sodium acetate is added to the diazo-solution in order to bind the excess of hydrochloric acid. The diazo-solution is then introduced, while stirring, into a solution of 13.8 grams of 2,3-hydroxynaphthoic acid-benzylamide in dilute caustic soda solution. The dyestufi which has separated is filtered by suction;

washed well and dried. It forms a red powder and corresponds with the following formula:

s omrzcm HaCO paper by means of sodium acetate and is introduced, while stirring, into a solution of 13.4 grams of 2,3-hydroxynaphthoic acid-cyclohexylamide in dilute caustic soda solution. The red dyestuff, thus formed, is filtered by suction, washed well and dried. It has the following formula:

SOzNHCaHa OH 9112 H2O CHZ H Hz ooNH CH2 It may be used in known manner for the preparation of lakes which are fast to oils and yield red tints of good fastness to light.

(3) A'pigment dye is prepared from 10.8 grams of 3-amino-4-methoxybenzene-l-sulfonic acidmethylamine and 17.8 grams of 6-bromo-2,3-hydroxynaphthoic acid-N-methyl-anilide in the manner described in Examples 1 and 2; it yields red lakes which are fast to oils and tolight.

(4) A pigment dye which is adapted for coloring rubber products is prepared as described in Example 1 from 12.9 grams of 3-amino-4-methoxybenzene-l-sulfonic acid-n-butyl-amide and 9.3 grams of 2,3-hydroxynaphthoic acid-amide. Thereupon, 4 per cent of the dyestufi is incorporated with a suitable mixture of crepe rubber, loading materials, sulfur and vulcanization accelerators and the whole is vulcanized in a vulcanization press for about 12 minutes at a steam pressure of 3 atmospheres above atmospheric pressure. There is obtained a vivid red vulcanizate which is very fast to light and neither bleeds nor gives rise to that phenomenon which is known as blushing or efflorescence when the rubber articles are stored.

(5) A pigment dye is prepared from 11.5 grams of 3-amino-4-ethoxybenzene-l-sulfonic acidmethylamide and 13.8 grams of 2,3-hydroxynapththoic acid-benzylamide, as described in Example 1. A mixture of crepe rubber, the usual admixtures and 4 per cent. of the aforesaid dyestufi is vulcanized in the cold by immersing it in a solution of sulfur chloride in benzine. The red mixture thus obtained is likewise fast to vulcanizationand very fast to light.

(6) By using in Example 4 a dyestuff prepared from 14.5 grams of 3-amino-4-methylbenzene-1- sulfonic acid-2',4'-dimethylanilide and 17.2 grams of 2,3-hydroxynaphthoic acid-N-cyclo-hexylanilide, and incorporating it with. a rubber product as described in Example 4, a red mixture is obtained which is fast to vulcanization and possesses a high fastness to light.

(7) The pigment dye of the following formula:

o ON prepared from 10.7 grams of 3-amino-4-methylbenzene-l-sulfonic acid-ethylamide and 12.7 grams of 2,3-hydroxynaphthoic acid-piperidide is incorporated with a rubber product in the manner indicated in Example 4. There is obtained a vivid orange mixture which is likewise fast to vulcanization and to light.

The following dyestuffs, among others, are capable of production in accordance with this invention:

Blaze-compound of: Coupled with: Shade:

3 amino 4 methyl- 2,3- hydroxynaphthoic benzene 1 sulfonic acidacid- 1 Amide 2 Methylamide 3 Benzylamide 4 Cyclohexylamide 5 6 7 8 Gyclohexylamide Red 9 1,2,3,4 tetrahydro- Red 2 aminonaphthalene. 2 methyl 3 chlor- Diethylamide Red anilide. 2,4 dimethy1-anilide Diphenylamide. Yellow-red Benzylamide N-methyl-anilide- Yellow-red 2 methyl 3 chlor- N-benzylanilide Red N -methy1anilide Red N-carbazole Red N-methyl-cyclohexyl- Red amide. Dibenzylamide Red N -benzy1-cyclohexy1- Red amide. l,2,3,4 tetrahydro Amide Red 2-aminonaphthalene. 1' amino l-methyl Amide Red naphthalene.

3 amino 4 methoxybenzene 1 sulionie acid- 21 Amide Amide Red 22 23 24 Ethylamida. 25 Cyelohexylamide Red 26 N-methylanilide Red 27 N-methylbenzylamide Red 28 N -cyclohexylanilide Red 29 3 amino 4 ethoxy- 1 -amino 1 -methyl- Red benzene 1 sulfonic naphthalene. acid-methyl-amide.

6- bromo-2,3-hydroxynaphthoic acid- 30 3 amino 4 methyl- Benzylamide Red benzene l sulionic acid-anilide. 31 3 amino 4 methoxy- Benzylamide Bluish-red benzene 1 sulfonicacid-anilide. 32 3 amino- 4 ethoxy- Benzylamide Blnish-red benzene l sulionic acid-ethyl-amide. 33 3 amino 4 methyl- 6 methoxy 2, 3hy- Bluish-red benzene 1 sulfonic droxy-naphthoic acid-anilide. acid benzylamide.

Since an object of the present invention is toproduce dyestuffs of good fastness properties which dyestuffs are insoluble in water, it is to be understood that the aromatic nuclei of the general formulae appearing in the appended claims do not contain any substituents which are known to render the dyestuffs soluble in water. Substituents'of this kind are, for instance, the sulfonic acid and carboxylic acid group.

I'claim:

1. The water-insoluble azo-dyestuffs of the following general formula:

wherein Y represents a member of the group consisting of hydrogen, bromine and methoxy, X stands for a member of the group consisting of alkyl or alkoxy, R, R1 and R2 each stand for a member of the group consisting of hydrogen, alkyl, aryl, aralkyl and hydroaryl, or R1 and R2 are connected with each other to form a heterocyclic ring system, one of the two radicals R1 and R2 not being allowed to stand for hydrogen in case the other radical represents an aryl group, yielding fast red lakes and, when mixed with rubber products, red dyeings of very good fastness to light and to vulcanization.

2. The water-insoluble azo-dyestufi of the fol- 30 lowing formula:

S OzN 04110 35 HaC O N II N 0 ONE:

yielding fast red lakes and, when mixed with rubher products, red dyeings of very good fastness to light and to vulcanization.

3. The water-insoluble azo-dyestuff of the following formula:

S0:NHOHg HaC O /GH: CON\ lowing formula:

yielding fast red lakes and, when mixed with rubber products, red dyeings of very good fastness to light and to vulcanization.

ERNST FISCHER. 

